WO2023092799A1 - 对电化学装置内部微观结构进行标记的方法和装置 - Google Patents
对电化学装置内部微观结构进行标记的方法和装置 Download PDFInfo
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- the invention relates to the field of electrochemical devices, in particular to a method and a device for marking the internal microstructure of an electrochemical device.
- An electrochemical device refers to a battery that can be reused. After the battery is discharged, the active material in the battery can be activated by charging, and the battery can continue to be used.
- One of the electrochemical devices is a battery made of positive electrode current collector, positive electrode active material, negative electrode current collector, negative electrode active material, conductive agent, electrolyte, separator and other accessories.
- the mainstream representative of this structure is lithium ion Battery. Lithium-ion batteries are widely used in various fields such as automobiles, electronics, and energy storage because of their high energy density. In the battery design process, it is very important to evaluate the electrochemical characteristics of the battery in advance to design a battery that meets the needs.
- the current mainstream electrochemical stage models include: three-dimensional model, mesoscopic scale model, particle stacking model, etc. These models need to obtain the geometric distribution information inside the electrode sheet before calculation, so as to predict the electrochemical performance of the battery, so accurate It is very important to obtain the distribution information of the microscopic geometric structure inside the electrode sheet.
- an embodiment of the present invention provides a method and device for marking the internal microstructure of an electrochemical device.
- a method for marking the internal microstructure of an electrochemical device comprising the following steps:
- each component of the battery is marked through the grid, so that the electrochemical performance of the battery can be accurately calculated using the electrochemical settlement model. It is especially important that the positive electrode particles inside the current lithium battery are irregular in shape and have pores inside. This method marks the coverage or boundary of the positive electrode particles. It not only meets the requirement of calculation accuracy, but also saves calculation resources.
- the partial area is the area between adjacent positive electrode current collectors and negative electrode current collectors, including a positive electrode coating, a separator, and a negative electrode coating.
- the positive electrode coating is at least composed of positive electrode particles, positive electrode conductors, and electrolytes.
- the negative electrode coating is at least composed of negative electrode particles, negative electrode conductive agent and electrolyte. Selecting the area between adjacent positive and negative current collectors for marking can not only accurately calculate the performance of the entire battery, but also save the number of marked nodes and save computing resources.
- each positive electrode particle or negative electrode particle obtains coordinate information of no less than 5 marked nodes.
- the positive electrode particles are aggregated primary positive electrode particles, and the negative electrode particles are negative electrode active material particles. Since the primary particles of the positive electrode are usually lithium salt particles, these particles will be agglomerated inside the battery. The applicant found that marking a single particle takes a considerable amount of time and is not conducive to subsequent calculations. However, marking the agglomerated particles is not as good as marking a single particle Accurate, but still able to accurately predict the electrochemical performance of the battery through the electrochemical model.
- the negative electrode particles are marked by grid nodes to mark the boundaries of the negative electrode particles
- the positive electrode particles, separator, conductive agent and electrolyte are marked by grid nodes of their coverage areas.
- negative electrode particles such as graphite, silicon carbon and other carbon materials commonly used at present
- they will not agglomerate in the electrolyte and appear as a single individual with clear and regular boundaries. Accurate overall coordinates can be obtained only by marking the boundaries information.
- the positive electrode particles especially the lithium salt type positive electrode particles commonly used at present, because they will agglomerate into larger positive electrode particles in the electrolyte, these particles are irregular in shape and have pores. For convenience.
- conductive agents and electrolytes their irregular shapes are also suitable for marking by covering methods.
- the negative electrode material or other materials are agglomerated in the electrolyte, and the primary particles of the positive electrode are separated from each other, then the negative electrode material can also be marked by marking the coverage area, and other materials with clear boundaries can be marked by marking the boundary. particles or components.
- the boundary marking grid node of the negative electrode particle is the closest grid node to the outside of the boundary of the conductive agent particle.
- some carbon materials such as graphite and silicon carbon are commonly used as negative electrode materials.
- the surface has outward protrusions, and the outer grid nodes are used for marking. Compared with the method of not distinguishing the inner and outer sides, only the grid nodes closest to the boundary are selected for marking. The solution results are more accurate.
- the geometric distribution state information of positive electrode particles, negative electrode particles, diaphragm, conductive agent and electrolyte of the electrochemical device is generated based on an algorithm or by scanning the real object with an electron microscope.
- the geometric distribution state information inside the battery can be generated through software algorithms based on the material information used, or it can be made into a real object and then scanned by an electron microscope to generate it.
- a device for marking the internal microstructure of an electrochemical device includes a memory and a processor, at least one program instruction is stored in the memory, and the processor loads and executes the at least A program instruction to implement the method for marking the internal microstructure of an electrochemical device according to the first aspect.
- the present invention uses grid software to mark the positive electrode particles, negative electrode particles, diaphragm, positive electrode conductive agent, negative electrode conductive agent and electrolyte respectively inside the battery, which improves the accuracy of the marking.
- the present invention uses the coverage area to mark the particles or components with blurred boundaries, and only marks the boundary of the boundary particles or object particles or components, so that the electrochemical model can calculate more accurate results based on these marking information, And it can save computing resources.
- the present invention adopts the method of marking the closest outer node, and the obtained node information can be solved by an electrochemical model to obtain a more accurate prediction result.
- the grid node coordinate information obtained, after being substituted into the electrochemical model can obtain a more accurate prediction of battery performance than other marking methods, and the calculation efficiency is more efficient.
- Fig. 1 is the structure of the internal parts of the lithium battery marked with the background grid in the present invention
- Fig. 2 is an enlarged view of part A in Fig. 1 .
- Embodiment As shown in Figure 1, it is a partial cross-sectional view of the interior of the battery generated by algorithm simulation, including a positive electrode current collector 1, a positive electrode coating 11, a separator 5, a negative electrode coating 21, and a negative electrode current collector 2 from top to bottom. , the positive electrode coating 11, the negative electrode coating 21 and the gaps of the separator 5 are filled with the electrolyte 4, wherein the positive electrode coating 11 is distributed with a positive electrode conductive agent 31, and the negative electrode coating 21 is distributed with a negative electrode conductive agent 32.
- the positive electrode coating 11 includes positive electrode particles 101 coated and solidified on the positive electrode current collector.
- the positive electrode particles are secondary aggregates formed after the primary active particles of the positive electrode lithium salt are agglomerated.
- the negative electrode coating 21 includes a coating And solidify the negative electrode particles 201 on the negative electrode current collector, the negative electrode particles are negative electrode carbon material active particles.
- the positive electrode coating 11 at least further includes a positive electrode conductive agent 31 and an electrolyte 4 filled in pores of the coating.
- the negative electrode coating 21 at least further includes a negative electrode conductive agent 32 and an electrolyte 4 filled in the pores of the negative electrode coating.
- the method for marking the internal microstructure of the electrochemical device of the present invention at least includes the following steps:
- the positive electrode particles are made of lithium
- the agglomerated particles of the positive electrode primary particles made of salt, and the negative electrode particles are carbon material active particles;
- the geometric distribution state information in the battery can also generate three-dimensional graphics.
- the negative electrode particle is marked by the grid node closest to the outside of the negative electrode particle 201 boundary
- the positive electrode particle is marked by the positive electrode particle 101 coverage area
- the separator is marked by the diaphragm coverage area
- the positive and negative electrode conductors are marked by the positive and negative electrode conductors
- the electrolyte coverage area is marked by the positive and negative conductive agent coverage area
- the grid density is such that the number of grid nodes marked by each positive electrode particle or negative electrode particle is about 500 to 1000;
- the size of the particles inside the battery is different, and the nodes required to mark the particles are also different.
- Quantitative coordinate information can be substituted into the electrochemical model to obtain more accurate electrochemical performance prediction data, and the grid density can be adjusted with grid generation software to meet the minimum number of marked grid nodes required for each positive electrode particle or negative electrode particle .
- the density of the background grid so that the number of labeled nodes for each positive electrode particle or negative electrode particle is between 500 and 10,000. It is understandable that the larger the number of nodes, the more accurate the performance prediction will be. However, when the number of nodes marked by a single particle is too large, for example, more than 100,000, the accuracy of the prediction will not be significantly improved. Instead, it will consume a lot of computing resources.
- the number of marked nodes can be adjusted by adjusting the density of the background grid; Screen some representative marked nodes to achieve the purpose of screening a small number of marked nodes at typical positions for accurate prediction. This method can be realized by image processing software.
- the number of labeled nodes is based on the number of labeled nodes for positive and negative particles.
- the coordinate information of all marked nodes can be obtained according to the needs, and the coordinate information of only some representative marked nodes can be selected for calculation.
- a device for marking the internal microstructure of an electrochemical device includes a memory and a processor, the memory stores at least one program instruction, and the processor loads and executes the at least one program instruction to realize the electrical A method for labeling the internal microstructure of chemical devices.
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Abstract
一种对电化学装置内部微观结构进行标记的方法和装置，用于模拟计算电化学装置的电化学性能。该方法包括：先获取电化学装置的至少部分区域的正极颗粒、负极颗粒、隔膜、正极导电剂、负极导电剂和电解质的几何分布状态信息，再基于获取的几何分布状态信息生成二维或三维图形，然后基于生成的图形利用网格生成软件生成背景网格，再通过网格节点标记负极颗粒、正极颗粒、隔膜、正极导电剂、负极导电剂和电解质的边界或者其覆盖区域，最后获取至少部分标记节点的坐标信息。该方法通过上述步骤对电池内部进行标记，获取网格节点坐标信息，代入电化学模型后，比其他标记方式能得到较为精确的预测电池性能，且计算效率更为高效。
Description
本发明涉及电化学装置领域，尤其是涉及一种对电化学装置内部微观结构进行标记的方法和装置。
电化学装置是指可以重复利用的，在电池放电之后可以通过充电方式使电池内的活性物质激活，而继续使用的电池。电化学装置中的其中一类是由正极集流体，正极活性材料，负极集流体，负极活性材料，导电剂，电解质和隔膜及其他附件制作而成的电池，这种结构的主流代表是锂离子电池。锂离子电池因为能量密度高，而被广泛的应用在汽车，电子，储能等各个领域。在电池的设计过程中，提前评估电池的电化学特性，从而设计出满足需求的电池非常重要。目前主流的电化学阶段模型包括：三维模型、介观尺度模型、颗粒堆叠模型等，这些模型在计算之前需要获取电极片内部的几何分布信息，以此来预测电池的电化学性能，因此准确的获取电极片内部微观几何结构分布信息非常重要。
为了克服现有技术中的缺陷，提高数值模拟的准确度和效率，本发明实施例提供了一种对电化学装置内部微观结构进行标记的方法和装置。
为达到上述目的，本发明采用的技术方案是：
第一方面，提供一种对电化学装置内部微观结构进行标记的方法，包括以下步骤：
获取电化学装置的至少部分区域的正极颗粒，负极颗粒，隔膜，导电剂和电解质的几何分布状态信息；
基于获取的几何分布状态信息，生成二维或三维图形；
基于生成的图形，利用网格生成软件生成背景网格；
通过网格节点标记负极颗粒，正极颗粒，隔膜，正极导电剂，负极导电剂和电解质的边界或者其覆盖区域；
获取至少部分标记节点的坐标信息。
通过上述方法，通过网格分别对电池各个组成部分进行标记，从而能够用电化学结算模型精确的计算出电池的电化学性能。尤其重要的是，目前锂电池内部的正极颗粒形状不规则其内部具有孔隙，本方法通过标记正极颗粒覆盖范围或者边界的方式进行标记。既满足了计算精度的要求，又能节省计算资源。
优选地，所述部分区域为相邻正极集流体和负极集流体之间的区域，包括正极涂层，隔膜，负极涂层，所述正极涂层至少由正极颗粒，正极导电剂，电解质组成，所述负极涂层至少由负极颗粒，负极导电剂，电解质组成。选择相邻正负集流体之间的区域进行标记，既能够准确的计算出整个电池的性能，也可以节约标记的节点数量，节约计算资源。
进一步地，在所述获取标记节点的坐标信息步骤中，每个正极颗粒或负极颗粒获取不少于5个标记节点的坐标信息。申请人发现在进行电化学结算时，每个正极颗粒或负极颗粒至少要获5个标记节点的坐标信息，才能够相对准确的计算出电池的电化学性能。
进一步地，所述正极颗粒为正极一次颗粒团聚后的颗粒，所述负极颗粒为负极活性材料颗粒。由于正极一次颗粒通常为锂盐颗粒，这些颗粒在电池内部会团聚，申请人发现标记单个颗粒需要耗费相当多的时间，且不利于后续的计算，但是标记团聚后的颗粒，虽然不如标记单个颗粒精确，却仍然能够通过电化学模型精确预测出电池电化学性能。
优选地，所述负极颗粒的标记方式为通过网格节点标记负极颗粒的边界，所述正极颗粒，隔膜，导电剂和电解质的标记方式为标记其覆盖区域的网格节点。对于负极颗粒的边界标记而言，例如目前常用的石墨，硅碳等其他碳材料，在电解质中不会团聚，呈单个个体，其边界清晰规则，只标记其边界即可得到准确的整体的坐标信息。而对于正极颗粒而言，尤其是目前常用的锂盐型正极颗粒，由于其在电解质中会团聚成更大的正极颗粒，这些颗粒形状不规则，且具有孔隙，通过覆盖网格节点进行标记更为方便。同样的，对于隔膜，导电剂和电解质而言,他们的形状并不规则，也适用于覆盖的方法进行标记。当然如果在一些应用中，负极材料或者其他材料在电解质中呈团聚状态，而正极一次颗粒相互分离，那么也可以通过标记覆盖面积的方式标记负极材料，用标记边界的方式标记其他具有清晰边界的颗粒或组成部分。
优选地，所述负极颗粒的边界标记网格节点为与导电剂颗粒边界外侧最接近的网格节点。负极材料目前常用石墨，硅碳等一些碳材料，表面具有向外的凸起，以外侧网格节点进行标记，相比不区分内外侧，只选取最近接边界的网格节点进行标记方法，其解算的结果更为准确。
进一步地，所述电化学装置的正极颗粒，负极颗粒，隔膜，导电剂和电解质的几何分布状态信息基于算法或用电子显微镜扫描实物生成。
电池内部的几何分布状态信息可以基于所使用的材料信息，通过软件算法生成，也可以做成实物之后由电子显微镜扫描实物生成。
另一方面，还提供了对电化学装置内部微观结构进行标记的装置，所述装置包括存储器和处理器，所述存储器中存储有至少一条程序指令，所述处理器通过加载并执行所述至少一条程序指令以实现所述第一方面的对电化学装置内部微观结构进行标记的方法。
本发明具有以下的优点：
1.本发明对电池内部的正极颗粒，负极颗粒，隔膜，正极导电剂,负极导电剂和电解质用网格软件分别进行标记，提高了标记的准确性。
2.本发明对于边界模糊的颗粒或组成部分采用覆盖区域进行标记，对于边界颗粒或物体颗粒或组成部分则只标记其边界，从而使得电化学模型能够依据这些标记信息解算出较为精确的结果，并且还能节约计算资源。
3.本发明对于具有表面凸起的负极颗粒，采用了最接近的外侧节点标记的方式，获取的节点信息能够通过电化学模型解算出更为精确的预测结果。
因此，通过本发明上述步骤对电池内部进行标记，获取的网格节点坐标信息，代入电化学模型之后，相比其他标记方式能够得到较为精确的预测电池性能，且计算效率更为高效。
为让本发明的上述和其他目的、特征和优点能更明显易懂，下文特举较佳实施例，并配合所附图式，作详细说明如下。
为了更清楚地说明本发明实施例或现有技术中的技术方案，下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本发明的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图。
图1是本发明用背景网格标记的锂电池内部部分区域的结构；
图2是图1中A部分的放大图。
以上附图的附图标记：1、正极集流体；2、负极集流体；11、正极涂层；101、正极颗粒；21、负极涂层；201、负极颗粒；31、正极导电剂；32、负极导电剂；4、电解质；5、隔膜；6、网格。
下面将结合本发明实施例中的附图，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
实施例：如图1所示，为由算法模拟生成的电池内部局部剖面图，从上到下依次为包括正极集流体1，正极涂层11，隔膜5，负极涂层21，负极集流体2，所述正极涂层11，负极涂层21以及隔膜5的空隙里面都充满了电解质4，其中正极涂层11内部分布有正极导电剂31，负极涂层21内部分布有负极导电剂32。
所述正极涂层11包括涂覆并固化在正极集流体上的正极颗粒101，所述正极颗粒为正极锂盐一次活性颗粒团聚后形成的二次团聚体，所述负极涂层21包括涂覆并固化在负极集流体上的负极颗粒201，所述负极颗粒为负极碳材料活性颗粒。所述正极涂层11至少还包括填充在涂层孔隙内的正极导电剂31，电解质4。所述负极涂层21至少还包括填充在负极涂层孔隙内的负极导电剂32，电解质4。
结合图1和图2，本发明的对电化学装置内部微观结构进行标记的方法至少包括以下步骤：
获取基于算法生成的电化学装置的相邻正负电极片之间的部分区域的正极颗粒，负极颗粒，隔膜，正极导电剂，负极导电剂和电解质的几何分布状态信息，其中正极颗粒为由锂盐制成的正极一次颗粒团聚后的颗粒，负极颗粒为碳材料活性颗粒；
基于获取的几何分布状态信息，生成二维图形；
上述生成图形的步骤中，电池内的几何分布状态信息也可以生成三维图形。
基于生成的图形，利用网格生成软件生成背景网格6；
通过负极颗粒201边界外侧最接近的网格节点标记负极颗粒，通过正极颗粒101覆盖区域标记正极颗粒，隔膜覆盖区域标记隔膜，正负极导电剂覆盖区域标记正负极导电剂和电解质覆盖区域标记电解质，所述网格密度使得每个正极颗粒或负极颗粒标记的网格节点的数量在500～1000个左右；
需要说明的是，由于颗粒大小的不同，以及锂盐制造的正极颗粒具有容易团聚的特点，因此电池内部颗粒的大小是不相同的，标记颗粒所需的节点也是不相同的，为了达到获取足够数量的坐标信息以代入电化学模型中获取较为准确的电化学性能预测数据，可以用网格生成软件调整网格疏密度，从而满足每个正极颗粒或负极颗粒所需标记网格节点的最少数量。申请人发现，单个颗粒标记节点数量的选择不应当少于5个，当单个颗粒标记节点少于5个时，预测精度会有较大的偏差。因此，背景网格的疏密度调整为每个正极颗粒或负极颗粒的标记节点数量在500～10000个之间是比较合适的。可以理解的是，节点数量越多，对于性能的预测会越准确，但是当单个颗粒标记节点数量过多，例如超过100000个时，所预测的精确度并没有明显的提升，反而要消耗非常大的计算资源。
此外，对于背景网格的设置，一方面可以通过调节背景网格的密度来调节标记节点的数量，另一方面，也可以将背景网格调成较密的状态，再获取大量的标记节点，最后筛选部分具有代表性的标记节点来达到筛选少量典型位置的标记节点来精确预测的目的，这种方式可以通过图像处理软件来实现。
此外，对于电解质，导电剂以及隔膜的标记节点数量以满足正极颗粒和负极颗粒标记节点的数量为基础。
对于正负极颗粒的标记而言，不同的材料体系颗粒性能可能会有差别，例如单晶正极颗粒，就不会产生团聚现象，此时，就可以对其边界进行标记。但是从微观结构上看，隔膜，正负极导电剂，电解质的形态还是不规则的，更适合用覆盖区域的方式进行标记。
最后获取所有标记节点的坐标信息。
基于上述获取的坐标信息代入电化学模型中，例如：三维模型、介观尺度模型、颗粒堆叠模型等电化学模型，同时带入其他物理量信息，例如温度，电流密度，电势等信息就可以通过电化学模型预测锂电池的电化学性能。
对于坐标信息的获取而言，正如前面所述，可以根据需要获取全部标记节点的坐标信息进行阶段，也可以只选择部分具有代表性的标记节点的坐标信息进行解算。
对电化学装置内部微观结构进行标记的装置，所述装置包括存储器和处理器，所述存储器中存储有至少一条程序指令，所述处理器通过加载并执行所述至少一条程序指令以实现对电化学装置内部微观结构进行标记的方法。
本发明中应用了具体实施例对本发明的原理及实施方式进行了阐述，以上实施例的说明只是用于帮助理解本发明的方法及其核心思想；同时，对于本领域的一般技术人员，依据本发明的思想，在具体实施方式及应用范围上均会有改变之处，综上所述，本说明书内容不应理解为对本发明的限制。
Claims (8)
- 一种对电化学装置内部微观结构进行标记的方法，该方法用于模拟计算电化学装置的电化学性能，其特征在于：包括以下步骤获取电化学装置的至少部分区域的正极颗粒，负极颗粒，隔膜，正极导电剂,负极导电剂和电解质的几何分布状态信息；基于获取的几何分布状态信息，生成二维或三维图形；基于生成的图形，利用网格生成软件生成背景网格；通过网格节点标记负极颗粒，正极颗粒，隔膜，正极导电剂，负极导电剂和电解质的边界或者其覆盖区域；获取至少部分标记节点的坐标信息。
- 根据权利要求1所述的对电化学装置内部微观结构进行标记的方法：其特征在于：所述部分区域为相邻正极集流体和负极集流体之间的区域，包括正极涂层，隔膜，负极涂层，所述正极涂层至少由正极颗粒，正极导电剂，电解质组成，所述负极涂层至少由负极颗粒，负极导电剂，电解质组成。
- 根据权利要求1所述的对电化学装置内部微观结构进行标记的方法，其特征在于：在所述获取标记节点的坐标信息步骤中，每个正极颗粒或负极颗粒获取不少于5个标记节点的坐标信息。
- 根据权利要求1所述的对电化学装置内部微观结构进行标记的方法，其特征在于：所述正极颗粒为正极一次颗粒团聚后的二次团聚体，所述负极颗粒为负极活性材料颗粒。
- 根据权利要求1或3或4所述的对电化学装置内部微观结构进行标记的方法，其特征在于：所述负极颗粒的标记方式为通过网格节点标记负极颗粒的边界，所述正极颗粒，隔膜，导电剂和电解质的标记方式为标记其覆盖区域的网格节点。
- 根据权利要求5所述的对电化学装置内部微观结构进行标记的方法，其特征在于：所述负极颗粒的边界标记网格节点为与负极颗粒边界外侧最接近的网格节点。
- 根据权利要求根据1所述的对电化学装置内部微观结构进行标记的方法，其特征在于：所述电化学装置的正极颗粒，负极颗粒，隔膜，导电剂和电解质的几何分布状态信息基于算法或用电子显微镜扫描实物生成。
- 一种对电化学装置内部微观结构进行标记的装置，其特征在于：所述装置包括存储器和处理器，所述存储器中存储有至少一条程序指令，所述处理器通过加载并执行所述至少一条程序指令以实现如权利要求1至7任一所述的对电化学装置内部微观结构进行标记的方法。
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